EP1843987A2 - Lead-free ferroelectric/electrostrictive ceramic material - Google Patents
Lead-free ferroelectric/electrostrictive ceramic materialInfo
- Publication number
- EP1843987A2 EP1843987A2 EP05851837A EP05851837A EP1843987A2 EP 1843987 A2 EP1843987 A2 EP 1843987A2 EP 05851837 A EP05851837 A EP 05851837A EP 05851837 A EP05851837 A EP 05851837A EP 1843987 A2 EP1843987 A2 EP 1843987A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- ceramic composition
- tio
- electrostrictive
- ceramic
- ferroelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62259—Fibres based on titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3267—MnO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
Definitions
- the present invention is directed to ferroelectric and electrostrictive ceramic materials, especially those being lead-free and showing very strong remnant polarization and massive pure electrostriction, especially in (Sr 5 Bi 5 Na)TiO 3 solid solutions.
- the composition of the present invention is further directed to a solid state solution of bismuth-sodium titanate and bismuth-strontium titanate.
- Ferroelectric materials show that the permanent electric dipole moment of materials can be reoriented by the application of an external electric field.
- the piezoelectric effect can be described in a simple way: electricity is generated when mechanical pressure is applied. Inversely, by applying an electric field to a piezo- element, a mechanical deformations result. This is referred to as the inverse piezoelectric effect.
- the inverse piezoelectric effect has sometimes been confused with the electrostrictive effect which occurs in solid dielectrics.
- the two effects differ in two important respects.
- the piezoelectric strain is proportional to the electric-field intensity and changes sign with it, whereas the electrostrictive strain is proportional to the square of the field intensity and therefore independent of its direction. Further, the piezoelectric strain is usually larger by several orders of magnitude than the electrostrictive strain, and the electrostrictive effect occurs simultaneously with the piezoelectric effect but may be ignored for practical purposes in many cases.
- the electrostrictive effect is significant and can be used for practical applications.
- PMN often, is referred to as an "Electrostrictive Ceramic".
- the electrostrictive effect has several unique advantages, such as less or no hysteretic loss up to high frequencies, being temperature-stable, and exhibiting a fast response time.
- lead-containing ferroelectric/electrostrictive materials such as PbZrO 3 - PbTiO 3 (PZT), Pb(Mg 1/3 Nb 2/3 )O 3 - PbTiO 3 (PMN - PT), and Pb(Zni /3 Nb 2/3 )O 3 - PbTiO 3 (PZN - PT) are produced every year for a large range of applications. Due to the toxicity of lead, alternative lead-free materials are highly desirable for environmental reasons.
- Some modified BNT ceramics manifest reasonable ferroelectric/piezoelectric properties, which make the material promising as a substitute for PZT. Since the late 1980s, efforts have been made to study the possibility of substitution of lead-free BNT for PZT. Simple perovskite compounds, like BaTiO 3 , PbTiO 3 , SrTiO 3 , etc., were used to modify the ferroelectric/piezoelectric properties of BNT. Nagata and Takenaka ("Effect of substitution on electrical properties of (Bii / ⁇ Na ⁇ TiOrbased lead-free ferroelectrics"; Proc. of 12th IEEE Int. Symp. on Applications of
- Ferroelectrics ed. Streiffer, S.K., Gibbons, BJ. and Trurumi, T.); vol. I, pp45-51; July 30 - August 2, 2000; Honolulu, Hawaii, USA.
- P r value 33.7 ⁇ C/cm 2 reported for (Bio. 5 Nao .5 )Ti ⁇ 3 systems, which appears to be one of the best result to date published in the literature for BNT- based materials.
- the present invention is the result of the discovery that lead-free materials can be produced that exhibit unexpected high ferroelectric and electrostrictive performance, as well as reasonable piezoelectric properties.
- the composition can be varied in its proportions to achieve different properties and functionalities, such as a very strong remnant polarization or massive pure electrostrictive strain with very high electrostrictive coefficient. This is achieved by modifying the polarization and strain behavior of solid solutions "(1-x) (Sr 1-LS yBI y )TiO 3 + x (Na 0-5 Bi 0-5 )TiO 3 " and "(1-x) (Sri -y Bi y )TiO 3 + x (Na 0 . 5 Bio.
- the present invention is a composition consisting of "a ferroelectric relaxor” + “a ferroelectric” and results in a high performance lead-free ferroelectric solid solutions.
- a lead-free ferroelectric relaxor material (Sr 5 Bi)TiO 3 can be employed in combination with (Na 0-S Bi 0-5 )TiO 3 .
- the compositions are represented by the formulae "(1-x) (Sr I-1 S yBIy)TiO 3 + x (Na 0 , 5 Bio.
- compositions can be employed with or without substituting K and/or Li at Na sites and/or Sn, Hf, Nb, and/or Ta at Ti sites; and/or the use OfMnO 2 , and/or CuO as dopants.
- the solid solutions are prepared by a solid state reaction method as is known in the art.
- the raw materials, SrCO 3 , TiO 2 , Bi 2 O 3 , Na 2 CO 3 are weighted according to compositions, and are ball-milled to reduce and blend the powders.
- the mixed powder was dried and calcined in air to 800 - 900 0 C for 2 - 4 hours. Then the powder was ball-milled again, and dried, and pressed into disks or rods, sintered in air at 1200 - 1300 0 C for 2 - 4 hours.
- Silver or gold electrodes were made and attached on two sides of the discs or rods. For piezoelectric measurement, a poling process is needed, which was done at 80 - 120 0 C for 15 minutes under a dc bias 50 - 100 kV/cm.
- Hysteresis loops and strain measurements were performed at room temperature using a modified Sawyer-Tower circuit, and a linear variable displacement transducer (LVDT) driven by a lock-in amplifier at 1 Hz, respectively.
- LVDT linear variable displacement transducer
- X-ray diffraction analysis shows that all compositions are single phase.
- Quasi-static piezoelectric constant was measured by using a d 33 meter.
- Dielectric constant measurements were performed on an HP 4284A LCR meter.
- Example 1 high ferroelectric remnant polarization solid solutions [0014] In materials with compositions of "(1-x) (Sr 1-LSy BIy)TiO 3 + x
- Example 2 high electrostrictive solid solutions
- a remnant polarization as high as ⁇ 51 ⁇ C/cm 2 (with a coercive field ⁇ 50 kV/cm) and a "purely" electrostrictive strain level ⁇ 0.1% at 80 kV/cm with a electrostrictive coefficient of Q 0.02 m 4 C "2 ; which are comparable with, or even higher than that of the lead-containing ferroelectric ceramics, such as PZT, PMN-PT and PZN-PT.
- the piezoelectric constant d 33 is of 80 - 120 pC/N measured by quasi-static method.
- the ceramic composition of the present invention can be employed as a ferroelectric device, an electrostrictive device, or a piezoelectric device.
- Specific applications would include ferroelectric random access memory, nonlinear optical device, electrostrictive actuator, positioning device for manufacturing, scanning probe microscope, surface acoustic wave device, and piezoelectric actuator, although the list is not exhaustive and would include other similar or like applications.
- the foregoing embodiments of the present invention have been presented for the purposes of illustration and description. These descriptions and embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above disclosure.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Semiconductor Memories (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62987204P | 2004-11-19 | 2004-11-19 | |
PCT/US2005/041902 WO2006060191A2 (en) | 2004-11-19 | 2005-11-18 | Lead-free ferroelectric/electrostrictive ceramic material |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1843987A2 true EP1843987A2 (en) | 2007-10-17 |
EP1843987A4 EP1843987A4 (en) | 2010-08-18 |
EP1843987B1 EP1843987B1 (en) | 2011-11-02 |
Family
ID=36565530
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05851837A Not-in-force EP1843987B1 (en) | 2004-11-19 | 2005-11-18 | Lead-free ferroelectric/electrostrictive ceramic material |
Country Status (6)
Country | Link |
---|---|
US (1) | US8043987B2 (en) |
EP (1) | EP1843987B1 (en) |
JP (1) | JP4792039B2 (en) |
CN (2) | CN102942360B (en) |
AT (1) | ATE532221T1 (en) |
WO (1) | WO2006060191A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113964266A (en) * | 2021-10-13 | 2022-01-21 | 中国科学院光电技术研究所 | Method for preparing high-performance bismuth-based lead-free piezoelectric actuator |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8736151B2 (en) * | 2006-09-26 | 2014-05-27 | Velos Industries, LLC | Electric generator |
US8643255B2 (en) * | 2008-03-18 | 2014-02-04 | Kyocera Corporation | Piezoelectric ceramic and piezoelectric element using the same |
JP5526945B2 (en) * | 2010-03-31 | 2014-06-18 | Tdk株式会社 | Piezoelectric composition, piezoelectric ceramic, vibrator, and ultrasonic motor |
JP2015137194A (en) * | 2014-01-21 | 2015-07-30 | エプコス アクチエンゲゼルシャフトEpcos Ag | Dielectric ceramic composition, dielectric element, electronic component and laminated electronic component |
JP2015137193A (en) * | 2014-01-21 | 2015-07-30 | エプコス アクチエンゲゼルシャフトEpcos Ag | Dielectric ceramic composition, dielectric element, electronic component and laminated electronic component |
CN103940365B (en) * | 2014-05-15 | 2017-01-11 | 黑龙江大学 | Method for measuring electrostrictive coefficients through linear frequency modulation multi-beam laser heterodyne |
JP6365126B2 (en) * | 2014-08-29 | 2018-08-01 | Tdk株式会社 | Piezoelectric composition and piezoelectric element |
JP2016060647A (en) * | 2014-09-12 | 2016-04-25 | エプコス アクチエンゲゼルシャフトEpcos Ag | Dielectric composition, dielectric element, electronic component, and laminated electronic component |
CN111875373B (en) * | 2015-05-27 | 2022-11-29 | 爱普科斯公司 | Dielectric composition based on bismuth sodium strontium titanate, dielectric element, electronic component and laminated electronic component thereof |
CN107851516B (en) * | 2015-07-17 | 2020-03-06 | 埃普科斯股份有限公司 | Dielectric composition, dielectric element, electronic component, and laminated electronic component |
KR102098869B1 (en) * | 2015-07-17 | 2020-04-08 | 티디케이 일렉트로닉스 아게 | Dielectric composition, dielectric element, electronic component and multilayer electronic component |
JP6588620B2 (en) * | 2015-07-17 | 2019-10-09 | ティーディーケイ・エレクトロニクス・アクチェンゲゼルシャフトTdk Electronics Ag | Multilayer ceramic capacitor |
CN106938929B (en) * | 2017-03-23 | 2020-08-14 | 同济大学 | Method for preparing room temperature high electric card effect leadless relaxation ferroelectric ceramic |
CN111039671B (en) * | 2019-12-30 | 2022-02-08 | 西安工业大学 | Composite for preparing ceramic material, preparation method thereof and ceramic capacitor |
US11819702B2 (en) | 2020-03-04 | 2023-11-21 | North Carolina State University | Perovskite materials and methods of making and use thereof |
CN111592352A (en) * | 2020-03-29 | 2020-08-28 | 成都迪迈斯科技有限公司 | High-performance potassium sodium niobate series lead-free electrostrictive ceramic and preparation and application thereof |
CN111574792B (en) * | 2020-04-02 | 2022-10-21 | 杭州电子科技大学 | Preparation method of lead-free antiferroelectric and polymer blended dielectric material |
CN111943668B (en) * | 2020-07-03 | 2022-09-13 | 成都宏科电子科技有限公司 | Medium-temperature sintered high-dielectric low-loss negative temperature compensation type porcelain and preparation method thereof |
CN113501711A (en) * | 2021-07-12 | 2021-10-15 | 内蒙古科技大学 | Multilayer ceramic capacitor based on energy storage and electric card refrigeration and preparation method thereof |
CN114149258B (en) * | 2021-12-29 | 2023-03-24 | 全球能源互联网研究院有限公司 | Piezoelectric ceramic with laminated structure and preparation method and application thereof |
CN114455945A (en) * | 2022-02-16 | 2022-05-10 | 陕西科技大学 | Ferroelectric antibacterial ceramic and preparation method thereof |
CN114702392B (en) * | 2022-04-26 | 2023-10-03 | 闽都创新实验室 | Metal molecule-free antiferroelectric solid solution, preparation method and application |
CN115368131B (en) * | 2022-09-06 | 2023-08-01 | 南京工业大学 | Strontium bismuth titanate based leadless relaxor ferroelectric film, preparation method and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1253122A1 (en) * | 2001-04-25 | 2002-10-30 | NGK Spark Plug Company Limited | Piezoelectric ceramic material |
US20030134738A1 (en) * | 2000-11-21 | 2003-07-17 | Masahito Furukawa | Piezoelectric ceramic |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09100156A (en) * | 1995-10-04 | 1997-04-15 | Nikon Corp | Dielectric porcelain composition |
US6004474A (en) * | 1997-03-28 | 1999-12-21 | Tdk Corporation | Piezoelectric ceramic composition |
US20020036282A1 (en) | 1998-10-19 | 2002-03-28 | Yet-Ming Chiang | Electromechanical actuators |
KR100314762B1 (en) * | 1998-02-27 | 2002-01-09 | 사토 히로시 | Piezoelectric Ceramics and Piezoelectric Device |
JP3671791B2 (en) * | 1999-02-08 | 2005-07-13 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric ceramic element using the same |
JP2001048642A (en) * | 1999-08-10 | 2001-02-20 | Ngk Spark Plug Co Ltd | Piezoelectric ceramics |
JP3775184B2 (en) * | 1999-08-31 | 2006-05-17 | 日本碍子株式会社 | Method for manufacturing piezoelectric body |
US6514427B2 (en) * | 1999-10-18 | 2003-02-04 | Matsushita Electric Industrial Co., Ltd. | Piezoelectric ceramic composition and piezoelectric element containing the same |
JP4510966B2 (en) * | 1999-11-19 | 2010-07-28 | 日本特殊陶業株式会社 | Piezoelectric ceramics |
EP1231192A1 (en) | 2001-02-08 | 2002-08-14 | Ngk Spark Plug Co., Ltd | Lead-free piezoelectric ceramic materials |
JP4398635B2 (en) * | 2002-09-24 | 2010-01-13 | 株式会社ノリタケカンパニーリミテド | Piezoelectric ceramics |
US7319081B2 (en) * | 2003-02-27 | 2008-01-15 | Tdk Corporation | Thin film capacity element composition, high-permittivity insulation film, thin film capacity element, thin film multilayer capacitor, electronic circuit and electronic apparatus |
-
2005
- 2005-11-18 US US11/719,411 patent/US8043987B2/en not_active Expired - Fee Related
- 2005-11-18 EP EP05851837A patent/EP1843987B1/en not_active Not-in-force
- 2005-11-18 WO PCT/US2005/041902 patent/WO2006060191A2/en active Application Filing
- 2005-11-18 AT AT05851837T patent/ATE532221T1/en active
- 2005-11-18 CN CN201210336994.5A patent/CN102942360B/en not_active Expired - Fee Related
- 2005-11-18 JP JP2007543294A patent/JP4792039B2/en not_active Expired - Fee Related
- 2005-11-18 CN CNA2005800397528A patent/CN101305480A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030134738A1 (en) * | 2000-11-21 | 2003-07-17 | Masahito Furukawa | Piezoelectric ceramic |
EP1253122A1 (en) * | 2001-04-25 | 2002-10-30 | NGK Spark Plug Company Limited | Piezoelectric ceramic material |
Non-Patent Citations (4)
Title |
---|
ELKECHAI O ET AL: "NA0.5BI0.5TIO3-K0.5BI0.5TIO3 (NBT-KBT) SYSTEM: A STRUCTURAL AND ELECTRICAL STUDY" PHYSICA STATUS SOLIDI (A). APPLIED RESEARCH, BERLIN, DE, vol. 157, no. 2, 16 October 1996 (1996-10-16), pages 499-506, XP001038796 ISSN: 0031-8965 * |
SAKATA K ET AL: "Ferroelectric and antiferroelectric properties of (Na0.5Bi0.5)TiO3-SrTiO3 solid solution ceramics" FERROELECTRICS UK, vol. 7, no. 1-4, 1974, pages 347-349, XP9135844 ISSN: 0015-0193 * |
See also references of WO2006060191A2 * |
TAKENAKA T ET AL: "PIEZOELECTRIC PROPERTIES OF (BI1/2NA1/2)TIO3-BASED CERAMICS" FERROELECTRICS,, vol. 106, 1 January 1990 (1990-01-01), pages 375-380, XP009024438 ISSN: 0015-0193 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113964266A (en) * | 2021-10-13 | 2022-01-21 | 中国科学院光电技术研究所 | Method for preparing high-performance bismuth-based lead-free piezoelectric actuator |
CN113964266B (en) * | 2021-10-13 | 2023-09-19 | 中国科学院光电技术研究所 | Method for preparing high-performance bismuth-based leadless piezoelectric driver |
Also Published As
Publication number | Publication date |
---|---|
US8043987B2 (en) | 2011-10-25 |
US20100009841A1 (en) | 2010-01-14 |
EP1843987A4 (en) | 2010-08-18 |
JP4792039B2 (en) | 2011-10-12 |
CN102942360B (en) | 2014-09-03 |
ATE532221T1 (en) | 2011-11-15 |
JP2008520541A (en) | 2008-06-19 |
WO2006060191A9 (en) | 2006-08-24 |
WO2006060191A2 (en) | 2006-06-08 |
CN101305480A (en) | 2008-11-12 |
EP1843987B1 (en) | 2011-11-02 |
CN102942360A (en) | 2013-02-27 |
WO2006060191A3 (en) | 2008-07-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8043987B2 (en) | Lead-free ferroelectric/electrostrictive ceramic material | |
Malik et al. | Thermal-stability of electric field-induced strain and energy storage density in Nb-doped BNKT-ST piezoceramics | |
Lin et al. | Structure and electrical properties of Bi0. 5Na0. 5TiO3–BaTiO3–Bi0. 5Li0. 5TiO3 lead-free piezoelectric ceramics | |
Wu et al. | Lead-free piezoelectric ceramics with composition of (0.97− x) Na 1/2 Bi 1/2 TiO 3-0.03 NaNbO 3-x BaTiO 3 | |
Li et al. | Electromechanical and dielectric properties of Na0. 5Bi0. 5TiO3–K0. 5Bi0. 5TiO3–BaTiO3 lead-free ceramics | |
US6004474A (en) | Piezoelectric ceramic composition | |
Chaiyo et al. | Lead-free (Ba, Ca)(Ti, Zr) O3 ceramics within the polymorphic phase region exhibiting large, fatigue-free piezoelectric strains | |
Zhao et al. | Improved temperature stability and high piezoelectricity in lead-free barium titanate-based ceramics | |
Yu et al. | Ultralow dielectric loss of BiScO3-PbTiO3 ceramics by Bi (Mn1/2Zr1/2) O3 modification | |
Perumal et al. | Investigations on electrical and energy storage behaviour of PZN-PT, PMN-PT, PZN–PMN-PT piezoelectric solid solutions | |
Chang et al. | The effects of sintering temperature on the properties of (Na0. 5K0. 5) NbO3–CaTiO3 based lead-free ceramics | |
Chang et al. | An investigation of (Na0. 5K0. 5) NbO3–CaTiO3 based lead-free ceramics and surface acoustic wave devices | |
US6897174B2 (en) | Dielectric material compositions | |
Duong et al. | Ferroelectric‒to‒relaxor crossover in KNN‒based lead‒free piezoceramics | |
Li et al. | Dielectric, ferroelectric and electric field-induced strain properties of (Pb1-xBax)(Zr1-yTiy) O3 ceramics | |
WO2017203211A1 (en) | Temperature stable lead-free piezoelectric/electrostrictive materials with enhanced fatigue resistance | |
Li et al. | Large pyroelectricity via engineered ferroelectric‐relaxor phase boundary | |
Grace et al. | Enhanced synthesis, structure, and ferroelectric properties of Nb-modified 1− x [Bi 0.5 (Na 0.4 K 0.1)(Ti 1− x Nb x)] O 3− x (Ba 0.7 Sr 0.3) TiO 3 ceramics for energy storage applications | |
Awan et al. | Structure, dielectric and ferroelectric properties of lead-free (Ba, Ca)(Ti, Zr) O3-xBiErO3 piezoelectric ceramics | |
Han et al. | A dielectric and ferroelectric solid solution of (1− x) BaSnO 3–x PbTiO 3 with morphotropic phase boundary | |
Ramam et al. | Barium modified lead lanthanum strontium zirconium niobium titanate for dielectric and piezoelectric properties | |
Boucher et al. | Influence of the niobium or fluorine dopant concentration on the properties of Mn-doped lead zirconate titanate ceramics | |
Wu et al. | Structure and electrical properties of MnO doped (Ba 0.96 Ca 0.04)(Ti 0.92 Sn 0.08) O 3 lead free ceramics | |
Takenaka | Bismuth-based piezoelectric ceramics | |
Lin et al. | Ferroelectric and piezoelectric properties of Bi0. 5 (Na0. 925− x− yLi0. 075KxAgy) 0.5 TiO3 lead-free ceramics |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20070518 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK YU |
|
DAX | Request for extension of the european patent (deleted) | ||
R17D | Deferred search report published (corrected) |
Effective date: 20080717 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01L 41/193 20060101ALI20080819BHEP Ipc: H01L 41/187 20060101AFI20080819BHEP |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20100719 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: H01L 41/193 20060101ALI20110224BHEP Ipc: H01L 41/187 20060101AFI20110224BHEP |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602005031033 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: C04B0035000000 Ipc: H01L0041187000 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C04B 35/475 20060101ALI20110415BHEP Ipc: H01L 41/187 20060101AFI20110415BHEP |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602005031033 Country of ref document: DE Effective date: 20111229 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20111102 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20111102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120302 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120203 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120302 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111130 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111130 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120202 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111130 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 532221 Country of ref document: AT Kind code of ref document: T Effective date: 20111102 |
|
26N | No opposition filed |
Effective date: 20120803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111118 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602005031033 Country of ref document: DE Effective date: 20120803 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120213 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20111102 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20141120 Year of fee payment: 10 Ref country code: DE Payment date: 20141216 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20141118 Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602005031033 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20151118 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160601 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151130 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230510 |
|
P02 | Opt-out of the competence of the unified patent court (upc) changed |
Effective date: 20230624 |
|
P02 | Opt-out of the competence of the unified patent court (upc) changed |
Effective date: 20230710 |